Cyanoalkylaminotriazines

ABSTRACT

A SUBSTITUTED S-TRIAZINE OF THE FORMULA:   2-X,4-R&#39;&#39;,6-R2-S-TRIAZINE   WHEREIN X IS HALOGEN, ALKOXY, OR ALKYLMERCAPTO, ALKYL IN ALKOXY AND ALKYLMERCAPTO HAVING 1 TO 6 CARBON ATOMS; R1 IS   -NH-(CH2)N-C(-R3)(-R4)-(CH2)M-CN   WHEREIN N AND M ARE ZERO OR 1 WITH THE PROVISION THAT ONLY ONE OF N AND M MAY BE ZERO; R3 AND R4 ARE THE SAME OR DIFFERENT AND ARE STRAIGHT-CHAIN OR BRANCHED-CHAIN ALKYL HAVING FROM 1 TO 4 CARBON ATOMS AND WHEREIN EITHER R3 OR R4 MAY ALSO BE HYDROGEN; AND R2 IS   -NH-R5   WHEREIN R5 IS HYDROGEN OR STRAIGHT-CHAIN OR BRANCHEDCHAIN LOWER ALKYL. THE COMPOUNDS ARE USEFUL AS PLANT GROWTH MODIFIERS AND ARE DISTINGUISHED BY A HIGH SELECTIVITY AND A RAPID DECOMPOSITION IN THE GROUND.

United States Patent O US. Cl. 260--249.8 26 Claims ABSTRACT OF THE DISCLOSURE 'A substituted s-triazine of the formula:

wherein X is halogen, alkoxy, or alkyl-mercapto, alkyl in alkoxy and alkylmercapto having 1 to 6 carbon atoms; R is wherein n and m are zero or 1 with the provision that only one of n and in may be zero; R and R are the same or different and are straight-chain or branched-chain alkyl having from 1 to 4 carbon atoms and wherein either R or R may also be hydrogen; and

wherein R is hydrogen or straight-chain or branchedchain lower alkyl.

The compounds are useful as plant growth modifiers and are distinguished by a high selectivity and a rapid decomposition in the ground.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of application Ser. No. 652,036, now abandoned, filed by the same inventor on July 10, 1967 for Novel cyanoalkylamino Substituted Triazines Having Plant Growth Regulating Action, now abandoned.

BACKGROUND OF THE INVENTION The invention relates to substituted s-triazine compounds and their use as growth modifiers for plants and in particular as herbicides.

s-Triazine compositions are known which in the 2- position either have an azidoor an alkylmercapto-group or a halogen atom and which in the 4-position are substituted by a cyanoalkylamino group which is attached to a primary carbon atom. These compositions as disclosed in Belgian Pat. 656,233 and 644,355 do not have any noteworthy herbicidal properties.

In Pat. 2,476,547, triazine compounds have also been disclosed which contain cyanoalkylamino groups of specific configurations. An example, for instance, is the compound 2-chloro 4 amino 6 cyanomethyl-amino-striazine.

These compositions are in use as fungicides and insecticides. However, their herbicidal action is so minor that they can destroy leaf fungus without damaging the plant itself.

It is therefore an object of the present invention to provide for compounds which can be used for modifying plant growth, and in particular as herbicides and which are distinguished both by ahigh selectivity and by a rapid decomposition in the ground.

SUMMARY OF THE INVENTION This object is met by a substituted s-triazine of the formula:

wherein X is halogen, alkoxy, or alkylmercapto, alkyl in alkoxy and alkylmercapto having 1 to 6 carbon atoms; R is wherein n and m are zero or 1 with the provision that only one of n and in may be zero; R and R are the same or different and are straight-chain or branched-chain alkyl having from 1 to 4 carbon atoms and wherein either R or R may also be hydrogen; and R is wherein R is hydrogen or straight-chain or branchedchain lower alkyl.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The term lower in connection with alkyl groups or the alkyl portion of other groups as used in the above summary of the invention and as used in the following description and the claims is to be understood to refer to groups having 1 to 6 carbon atoms. Preferably, the groups have 1 .to 4 carbon atoms.

If X in the above-given formula is halogen it is preferably chlorine. A further preference for X is a lower alkoxy or alkylmercapto group.

If R and R are substituted alkyl or alkenyl groups, the substituents may be the following groups: OH, OR, SR or CN. R in these groups is again a lower alkyl group.

Starting materials colorless liquid, B.P. 70-7l C.

colorless liquid, B.P. 8l-82 C.

For instance, if allylcyanide is reacted with concentrated ammonia (40%) in an autoclave for a period of 2 hours, 3-amino-butyronitrile is obtained of the following formula:

colorless liquid, B.P. 68-69 C.

In general, compounds of the following formula (colorless liquid B.P. 66-68 C.)

are obtained likewise by reacting 2,2-dialkylated acrylonitrile with ammonia. The necessary acrylonitriles can he formed by Knoevenagel-condensation of ketones with cyanoacetic acid and subsequent decarboxylation.

Compounds of the type CH; NG( ]-(CH ),.NH

are for instance obtainable as follows CH3 CHaNOg 011 00011 CH C( 3CH;N0,

CH3 CH; OH;

| KON l I H;CCCH;NO, HaCCCH NO H CCCH NH,

C OCHa (IJN red (IJN Process of making the compounds The compounds of the invention can for instance be made as follows: 1 mole of cyanuric chloride may for instance be reacted with 1 mole of an aminonitrile in the presence of 1 mole of a hydrogen halide binding agent such as sodium hydroxide, and this may then be followed by reaction with 1 mole of ammonia or an amine of the general formula NHR R likewise in the presence of 1 mole of sodium hydroxide. It is also possible first to introduce the amine of the formula NHR R and subsequently to react with the aminonitrile.

The thus-obtained 2-c'hloro-cyanoalkylamino-6-(a1kyl)- aminotriazines can then be converted to the corresponding alkylmercapto compounds by reaction with alkylmercaptans in the presence of an acid receptor. The corresponding alkoxy compounds, on the other hand, can be formed by reacting the halogeno triazines with a sodium alcoholate.

Utility The compounds of the invention are effective plant growth modifiers and, in particular, herbicides and are distinguished by a high selectivity and a rapid decomposition in the ground. The compounds may be used in view of their superior herbicidal properties both before and after germination. They will affect the plant growth even in very small concentrations. Depending on the type of R to R substituents, they can be used for destroying or selectively suppressing weeds from an environment of cultivated plants, or they may serve to completely destroy or prevent undesirable plant growth.

The compounds of the invention can also be used for defoliation, for reduction of the fruition, delayed blossoming, etc. They can be used singly or in a mixture of different compounds of the invention or in a mixture with other type herbicides. They can also be used in admixture with insecticides, fungicides and fertilizers.

It was surprising that the compounds of the invention had such strong herbicidal action and such high selectivity in spite of the fact that they had only a comparatively small survival time in the ground amounting only to a few months, which is particularly important in case of rotating crops.

As already indicated, the compounds of the invention, depending on the substituents present, have excellent preemergence or postemergence activit or an activity of both types together. In most cases, they are crystalline compounds and have a high solubility in many organic solvents. This distinguishes the compounds from many prior-art chloro-bis-alkylaminotriazines which have only slight solubility in customary solvents. The compounds of the invention can therefore be used very well for spraying by airplanes in the form of solutions.

Suitable solvents are for instance the following: alcohols, ketones, hydrocarbons, halogenated hydrocarbons such as chloronaphthalene, mineral oils such as diesel fuel, vegetable oils or mixtures of these several materials.

The compounds of the invention can also be used on solid carrier materials. 'Examples of such carrier materials are clay, kaolin, diatomaceous earth, bentonite, talcum,

finely ground calcium carbonate, charcoal, sawdust, etc.

The effective agents can be mixed in dry form with the carrier materials. However, they can also be applied to the carrier materials as solutions or emulsions or can be mixed with the carrier materials in this form subsequent to drying of the mixture.

In order to improve the adherence of the effective agents on the carrier materials, conventional adhesives may be used such as glue, casein, aliginic acid and similar materials.

It is finally also possible to mix the compounds of the invention, if desired together with carrier materials, with emulsifying agents and stabilizers, for instance to form a paste or a powder which then may be set up with water to form a suspension.

Suitable cross-linking agents, emulsifiers and stabilizers are anionic, cationic or non-ionic materials of the conventional types such as Turkey red oil, fatty acid salts, alkylarylsulfonates, secondary alkylsulfates, resin acid salts, polyethylene ethers of fatty alcohols, fatty acids or fatty amines, quarternary ammonium compounds, ligninsulfone acid, saponin, gelatin, casein. These additives may be used singly or in mixture of different additives.

Specific examples and tests Examples for the compounds of the invention are listed in the following Table I. All of the compounds comply with the general formula:

6 diatomaceous earth were ground to extreme fineness as in a ball mill. They were then useful as a dusting composition.

Example 3 5 f A mixture of 2 1sopropylamino-4-(1,1-dimethyl-2- C cyano-ethyl)-amino-6-methy1mercapto-s-triazine, 70 parts of xylene and 10 parts of octylphenylpolyglycolethers p) from dl-t-butylphenol and 10-12 moles ethylenexodie X- G- 10 Hostapal CV) was formed, to which water was N then added to prepare a stable emulsion.

TABLE I X R R2 Color and form M.P. C.)

01 (FE: N Hz White crystals 228-229 NHCHzCH-CN C] CzI-I5 NH2 -dO 201-302 NHCHzCH-CN 01 Same as above NHCHa d0 208-209 01 do NHC2H5 d0 188-189 01 do NH 031174 do 88-89 Cl (3H3 NH 02115 .1.. d0 141-143 NHCHGHzCN 01 Same as above NHCaH'l-l .do 183-184 or (IE NH 02115 ...do 125-127 NH-(|JCH2-GN 01 Same as above NHCsHi-l do 168-169 Cl .do NHCHa .d0 155-157 01 ?Ha NH CzHs ..d0 168-169 NH-CH2?-CN CHa SCHz (3H3 NHCzHa Light yellow crystals.-. 110-111 NH-OHz-CHCN SCH; Same as above- 00H: do H OOHa do. OCH: .(1O NHCaH'l-i SCH (llHa NHCHCH2CN OOH; Same as above NHCzHa do 89-90 8011 (3H3 NHC2H5 Light yellow crystals 113 NH(\3CHz-CN 0011;; Same as above NHCzHs White crystals 156 More specific examples including the process of making are the following:

Example 1 10 parts of 2-ethylamino-4-(Z-cyano-propyl)-amino-6- chloro-triazine, 89 parts bentonite and 1 part of a. highly dispersed pyrogenically formed silicic acid were ground in a ball mill to a fine dust. This mixture could then be used as a dusting powder.

Example 2 A mixture of 2 isopropylamino-4-(1,1-dimethyl-2- Example 4 50 parts of 2-ethylamino-4-(Z-cyano-propyl)-amino-6- methoxy-s-triazine were dissolved in 450 parts of kerocyanoethyl)-amino-6-methoxy-s-triazine and 90 parts of sene. The solution could immediately be used for spraying.

Example 6 67 g. of methacrylonitrile and 200 ml. of concentrated.

ammonia (23%) were introduced in a 1 liter autoclave. There was further introduced 200 g. of ammonia gas and the mass was then rapidly heated to 150 C. After 2 hours, it was gradually cooled down, the pressure was released and the homogeneous aqueous solution was saturated with potassium hydroxide. The amine was separated out, dried with potassium hydroxide and subsequently distilled in a vacuum. 1-methyl-2-arninopropionitrile distilled at B.P. 707l C. as a colorless liquid. The yield was 61.5 g. corresponding to 73.2% of the theoretical yield.

Example 7 A mixture of 67 g. of allylcyanide and 250 g. of an aqueous ammonia solution (40%) was heated in an autoclave for 3 hours to 140-150 C. upon shaking, After cooling, the aqueous solution was saturated with potassium hydroxide, the precipitated amine was separated, dried with potassium hydroxide and distilled in a vacuum. 3-amino-butyronitrile distilled at B.P. 6869 C. as a colorless liquid. The yield was 64.7 g., corresponding to 77% of the theoretical yield.

Example 8 1-cyano-2-methyl-crotonic acid was decarboxylated by a heat treatment to 2,2-dimethyl-acrylonitrile. The crotonic acid had been obtained by Knoevenagel-condensation from cyanoacetic acid and acetone.

81 g. of the nitrile were then heated together with 250 g. of a 50% aqueous ammonia solution for 3 hours in an autoclave to a temperature between 140 and 150 C. Subsequently, the mass was cooled, then saturated with potassium hydroxide, and the formed amine was separated. The amine was dried with potassium hydroxide and distilled in a vacuum, 64.8 g. of 2-amino-2,2dimethyl-propionitrile distilled at B.P. 66-68 C. as a colorless liquid which corresponded to 66.3% of the theoretical yield.

Example 9 184.5 g. of cyanuric chloride were suspended in 600 ml. acetone, then cooled to C. 200 g. of ice was added. Thereafter, 84 g. of 1-methyl-2-amino-propionitrile were added dropwise at 0-2 C. and subsequently a solution of 40 g. NaOH was added in 200 ml. H 0. 2 mole of a 50% ethylamine solution (180 g.) were then added dropwise at a temperature up to 40 C. The acetone was removed in a vacuum as soon as the solution had a neutral reaction (after about 1 hour) and the solution was then diluted with water. The white crystals were removed by suction, washed and dried at 50 C. in a vacuum. The thus-obtained 2 ethylamino-4-(2-cyano-propyl)-amino-6- chloro-s-triazine had a melting point between 219 and 220 C. The yield was 238 g. which was equivalent to 99% of the theoretical yield.

Example 10 24.05 of the chlorotriazine mole) which was obtained in Example 9 was subjected to boiling for 8 hours with a solution of 6.6 g. of sodium methylmercaptide in 200 ml. methanol. The solution subsequently was concentrated to dryness by evaporation and the residue was taken up with water. The crystalline product was removed by suction and dried. There were obtained light-yellow crystals of 2-ethylamino 4 (2-cyano-propyl)amino-6 methylmercapto-s-triazine with a melting point between 110 and 111 C. The yield was 22.5 g. corresponding to 85.2% of the theoretical yield.

Example 11 22.65 g. of 2-methylamino-4-(2-cyano-propyl)-amino- 6-chloro-s-triazine mole) were boiled for 6 hours with a solution of 5.4 g. of sodiummethylate in 150 ml. methanol. The mixture then had a neutral reaction. It

was evaporated to /3 of its initial volume, whereupon it was poured into water. The precipitated highly viscous materials resulted in rapid crystallization. After separation and drying, there were obtained 19.9 g. of 2-methylamino-4-(2-cyano propyl) amino-6-methoxy-s-triazine in the form of white crystals, that is 89.8% of the theoretical yield, having a melting point of 106 C.

Example 12 55.35 g. of cyanuric chloride were suspended in 300 ml. acetone, cooled to 0 C. and, at this temperature, 25.7 g. of 3-amino-butyronitrile were added upon stirring. A solution of 12 g. NaOH in 60 ml. water was subsequently added. Thereafter, 25.5 g. of a 70% isopropylamine solution was added dropwise and finally another solution of 12 g. of NaOH in 60 ml. H O were added at a temperature rising up to 45 C. As soon as the mixture had a neutral reaction, the acetone was removed in a vacuum, and the residue taken up with water. The white crystals were removed by suction, washed and dried. The formed 2-isopropyl-amino-4-(l-methyl 2 cyano-ethyl)-aminochloro-s-triazine has a melting point between 183 and 184 C. The yield was 75 g. corresponding to 98% of the theoretical yield.

Example 13 184.5 g. of cyanuric chloride were suspended in 600 ml. acetone. The mixture was cooled to 0 C. Thereafter, 99 g. of 2,2-dimethyl-Z-amino-propionitrile were added dropwise at this temperature and subsequently 200 ml. of a 5-normal sodium hydroxide solution were added. The mixture soon had a neutral reaction. At a temperature rising to 40 C. g. of a 50% ethylamine solution and 200 ml. of 5 N sodium hydroxide solution were added. The neutral solution was diluted with 2 liters of water and the crystals were removed by suction. After drying, there were obtained 238.5 g. of 27. The yield was 93.75 of the theoretical yield. The melting point was between 125 and 127 C.

Example 14 A solution of 18.45 g. of cyanuric chloride in ml. tetrahydrofuran was treated at 0 C., first with 9.9 g. 1,l-dimethyl-2-aminopropionitrile and, secondly, with 20 ml. 5 N sodium hydroxide solution. As soon as the solution had a neutral reaction, 9 g. of a 50% ethylamine solution were added at a temperature up to 40 C. and finally 20 ml. 5 N NaOH were also added. There were obtained 22.9 g. of 2-ethylamino-4-(2,2-dimethyl-2- cyanoethyl)-amino-6-chloro-s-triazine which corresponded to 89.7% of the theoretical yield, in the form of white crystals with a melting point between 168 and 169 C.

Example 15 Tests In order to test the herbicidal action of the compounds of the invention, the following experiments were carried out:

(A) Application to the ground after seeding:

Various seeds were embedded by raking into the earth which was contained in plastic bowls. The test was carried out in a hothouse at a temperature of 21 C. The earth was watered in the morning and in the afternoon and was then treated with a dispersion which was obtained by pouring a solution of the herbicide into equal parts of water. Then normal watering was continued, and the germinating of the plants was checked. Two weeks after seeding, it was determined whether and to what extent the plant growth had been suppressed.

(B) Application to the ground after germination:

Various seeds were again placed into the earth by raking in a hothouse having an interior temperature of 21 C. After germinating, the aqueous dispersion mentioned at A of the effective agent of the invention was applied TEST SERIES B.C011tinue(l Rye- Liu- Mus- Sugar kgJha. Corn Oats grass Peas seed tard beets The results of the tests will be found in the following Table Th evaluation of the growth wa i d t on a scale on which zero indicated normal growth and 9 total destricution of the plant. -"fi The concentration of the effective agent in the different test series was as follows:

TES'I SERIES (3 Rye- Lin- Mus- Sugar kgJha. Corn Oats grass Peas seed tard beets (A) kg./ha. and 1 kg./ha. (B) 10 kg./ha., 1 kg./ha., 0.1 kg./ha. (C) 10 kg./ha., 1 kg./ha., 0.1 kg./ha. 15

Compound ha in these statements refers to one hectare equalling number .mm as a m N S U10 2 2 C n H H z 06 O C H w a a a s n HHHHH H O OC CC C C .mu m a a a e m m m N N N m .n f M m um H 5 m L o C 0 ems mm m m e u T mm m e m 1 1 1 c X0 0 0 Hr. l

e .w n u n s es 0 U u a: m n n mum m 1 mm m w 4 a m. I 2 a t T On I. H H

NHOrH NHCaHs NHOH:

NHCzHs NHCnHs TEST SERIES A RyekgJha. Corn Oats grass Peas IV OCHa V OCHa VI OCH;

VII SCH;

VIII... SCH;

0 101 1010101 .Z W W 2 mm 2 2 2 3. The compound as in claim 1, wherein X is lower alkoxy or lower alkylmercapto. TEST SERIES B 4. The compound of claim 1, in which X 1s Cl and 1n Rye- Lin- Mus- Sugar which R1 is kgJha. Corn Oats grass Peas seed tard beets H Compound number NHCH H-C N and R is NH 5. The compound of claim 1, in which X is Cl and in which R is E NH0H,CH0N

mimim am 0 0 0 0 5 and R is NHCH 6. The compound of claim 1, in which X is Cl and in which R is NH=CH;CHCN

and I{2 is 7. The compound of claim 1, in which X is Cl and in which R is a -HCH;C H- C N and 1{ is NHc3H7-l.

8. The compound of claim 1, in which X is Cl and in which R is CZH5 NI-ICH;CHCN and R is NH 9. The compound of claim 1, in which X is Cl and in which R is E NHCH;CHCN

and R is NHCH 10. The compound of claim 1, in which X is Cl and in which R is NHCHgCH-CN and R is NHC H 11. The compound of claim 1, in which X is Cl and in which R is NH-GH,-CHCN and R is NHC H -i.

12. The compound of claim 1, in which X is Cl and in which R is w NH-0HCH,CN

and R is NHC H 13. The compound of claim 1, in which X is Cl and in which R is W NHoH-CH,-CN

and R2 iS NHC3H7'l.

14. The compound of claim 1, in which X is Cl and in which R is E NH?CH CN and R is NHC H 15. The compound of claim 1, in which X is Cl and in which R is NH-C-CH CN and R is NHC H -i.

16. The compound of claim 1, in which X is Cl and in which R is (3H NH-(f-CH -CN and R is NHCH 17. The compound of claim 1, in which X is Cl and in which R is NH-CH, I CN and R2 is NHC2H5.

18. The compound of claim 1, in which X is SCH and in which R is i NH-CHg-CH-CN and R is NHC H 19. The compound of claim 1, in which X is SCH and in which R is (3H3 NHCH,-CHCN and R is NHc H -i.

20. The compound of claim 1, in which X is OCH and in which R is CH, NHCH;(|JHCN and R is NH 21. The compound of claim 1, in which X is OCH and in which R is i NHCH;CHCN

and R is NHCH 22. The compound of claim 1, in which X is OCH and in which R is NHCI'ICHZCN and R is NHCzHq-i.

23. The compound of claim 1, in which X is SCH and in which R is (111 NH-CH -CHr-CN and R is NHC H 24. The compound of claim 1, in which X is OCH and in which R is CH NH-(IJHCHQCN and R is NHC H 25. The compound of claim 1, in which X is SCH and in which R is (3H3 NH(IJCH2CN and R is NHC H 26. The compound of claim 1, in which X is OCH and in which R is 5 NHo|CH,-CN

CH and R is NHC H References Cited UNITED STATES PATENTS 3,255,191 6/1966 Dexter et al. 260249.8 X 3,305,551 2/1967 Picklesimer et al. 260249.8 X 3,326,913 6/1967 Schulz et al. 260249.6 3,415,827 12/1968 Nikles et al. 260249.8

JOHN M. FORD, Primary Examiner US. Cl. X.R.

7l93; 260249.6, 465.1, 465.5 R, 638 N 

